The shortage of fresh water resources resultes from the rapid growth of population and industrial development. Desalination of seawater and brackish water is an effective way to alleviate the freshwater crisis. In this work, the TiO₂/Ti₃C₂T_x composites were prepared by directly calcinating Ti₃C₂T_x for hybrid capacitive deionization (HCDI). The results show that the calcination temperature has a significant impact on morphology, structure, electrochemical and desalination behavior of the TiO₂/Ti₃C₂T_x composites. To constitute the full HCDI device, the optimized TiO₂/Ti₃C₂T_x and acid treated activated carbon (AC) was employed as cathode and anode, respectively. In the constant voltage mode, the salt removal capacity of TiO₂/Ti₃C₂T_x‖AC reached 23.8 mg·g ^-1 under the cell voltage of 1.2 V in NaCl solution with an initial conductivity of 3000 μS·cm ^-1. After 20 cycles, the capacity retention rate remains at 78%. Besides, through exploring the morphology and crystal texture evolution of TiO₂/Ti₃C₂T_x electrodes before and after desalination, it is found that the desalination of TiO₂/Ti₃C₂T_x electrodes may be achieved due to the intercalation of sodium ions into the Ti₃C₂T_x interlayer.